Nanotribological Printing: A Nanoscale Additive Manufacturing Method.

Additive manufacturing methods are transforming the way components and devices are fabricated, which in turn is opening up completely new vistas for conceiving and designing products and engineered systems. Small-scale (submicrometer) additive manufacturing methods are largely in their infancy. While a number of methods exist, a particular challenge lies in finding methods that can produce a range of materials while obtaining sufficiently robust mechanical properties. In this paper, we describe a novel nanoscale additive manufacturing technique deemed "Nanotribological Printing" (NTP), which creates structures through tribomechanical and tribochemical surface interactions at the contact between a substrate and an atomic force microscope probe, where material pattern formation is driven by normal and shear contact stresses. The "ink" consists of nanoparticles or molecules dispersed in a carrier fluid surrounding the atomic force microscope (AFM) probe, which are entrained into the contact during sliding. Being stress-driven, patterning only occurs locally within regions which experience contact and sufficiently high stresses. Thus, imaging and measurement to characterize the morphology and properties of the deposited structures can be conducted in situ during the manufacturing process. Moreover, using local mechanical energy as the kinetic driver activating the solidification process, the method is compact and does not require application of a bias voltage or laser exposure and can be performed at ambient temperatures. We demonstrate (1) control of pattern dimensions with sub-100 nm lateral and sub-5 nm thickness control through variations in contact size and applied stress, (2) creation of amorphous, polycrystalline, and nanocomposite structures including sequential multimaterial deposition, and (3) formation of manufactured structures which exhibit mechanical properties approaching those of bulk counterparts. The ability to create nanoscale patterns using standard AFM cantilever probes and operation modes (contact mode scanning in fluid) with commercial AFM instruments, independent of substrate, establishes NTP as a versatile and easily accessible method for nanoscale additive manufacturing.

Structure-property relationships from universal signatures of plasticity in disordered solids.

When deformed beyond their elastic limits, crystalline solids flow plastically via particle rearrangements localized around structural defects. Disordered solids also flow, but without obvious structural defects. We link structure to plasticity in disordered solids via a microscopic structural quantity, "softness," designed by machine learning to be maximally predictive of rearrangements. Experimental results and computations enabled us to measure the spatial correlations and strain response of softness, as well as two measures of plasticity: the size of rearrangements and the yield strain. All four quantities maintained remarkable commonality in their values for disordered packings of objects ranging from atoms to grains, spanning seven orders of magnitude in diameter and 13 orders of magnitude in elastic modulus. These commonalities link the spatial correlations and strain response of softness to rearrangement size and yield strain, respectively.

Tribology. Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts.

Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation.

Angle-resolved environmental X-ray photoelectron spectroscopy: a new laboratory setup for photoemission studies at pressures up to 0.4 Torr.

The paper presents the development and demonstrates the capabilities of a new laboratory-based environmental X-ray photoelectron spectroscopy system incorporating an electrostatic lens and able to acquire spectra up to 0.4 Torr. The incorporation of a two-dimensional detector provides imaging capabilities and allows the acquisition of angle-resolved data in parallel mode over an angular range of 14° without tilting the sample. The sensitivity and energy resolution of the spectrometer have been investigated by analyzing a standard Ag foil both under high vacuum (10(-8) Torr) conditions and at elevated pressures of N(2) (0.4 Torr). The possibility of acquiring angle-resolved data at different pressures has been demonstrated by analyzing a silicon/silicon dioxide (Si/SiO(2)) sample. The collected angle-resolved spectra could be effectively used for the determination of the thickness of the native silicon oxide layer.

Preventing nanoscale wear of atomic force microscopy tips through the use of monolithic ultrananocrystalline diamond probes.

Nanoscale wear is a key limitation of conventional atomic force microscopy (AFM) probes that results in decreased resolution, accuracy, and reproducibility in probe-based imaging, writing, measurement, and nanomanufacturing applications. Diamond is potentially an ideal probe material due to its unrivaled hardness and stiffness, its low friction and wear, and its chemical inertness. However, the manufacture of monolithic diamond probes with consistently shaped small-radius tips has not been previously achieved. The first wafer-level fabrication of monolithic ultrananocrystalline diamond (UNCD) probes with <5-nm grain sizes and smooth tips with radii of 30-40 nm is reported, which are obtained through a combination of microfabrication and hot-filament chemical vapor deposition. Their nanoscale wear resistance under contact-mode scanning conditions is compared with that of conventional silicon nitride (SiN(x)) probes of similar geometry at two different relative humidity levels (approximately 15 and approximately 70%). While SiN(x) probes exhibit significant wear that further increases with humidity, UNCD probes show little measurable wear. The only significant degradation of the UNCD probes observed in one case is associated with removal of the initial seed layer of the UNCD film. The results show the potential of a new material for AFM probes and demonstrate a systematic approach to studying wear at the nanoscale.

Transformations in wrinkle patterns: cooperation between nanoscale cross-linked surface layers and the submicrometer bulk in wafer-spun, plasma-treated polydimethylsiloxane.

We demonstrate control of the topography of strain-induced wrinkle patterns through the interplay between the bulk and the nanoscale cross-linked top layer of plasma treated, spin-coated polydimethylsiloxane (PDMS) thin films. The different morphological phases observed, varying from herringbones to caps, are in agreement with recent theoretical predictions. The cap phase exhibits short-range 3-fold-symmetric close-packed self-organization, demonstrating a bottom-up pathway toward the wafer-scale production of ordered, nanoscale patterns on surfaces.

Origin of ultralow friction and wear in ultrananocrystalline diamond.

The impressively low friction and wear of diamond in humid environments is debated to originate from either the stability of the passivated diamond surface or sliding-induced graphitization/rehybridization of carbon. We find ultralow friction and wear for ultrananocrystalline diamond surfaces even in dry environments, and observe negligible rehybridization except for a modest, submonolayer amount under the most severe conditions (high load, low humidity). This supports the passivation hypothesis, and establishes a new regime of exceptionally low friction and wear for diamond.